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    United States Patent Blackburn et aI. Patent Number: Date of Patent: PROCESS FOR THE PREPARATION OF 3(METBYltho) PROP ANAL AND 2BYDROXY-4-(METBYLTHIO) BUTANENITRILE. 260 / 601 FOREGN PATENT DOCUMENTS OTHER PUBLICATIONS.

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    United States Patent Blackburn et aI. Patent Number: Date of Patent: PROCESS FOR THE PREPARATION OF 3(METBYltho) PROP ANAL AND 2BYDROXY-4-(METBYLTHIO) BUTANENITRILE. 260 / 601 FOREGN PATENT DOCUMENTS OTHER PUBLICATIONS.

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    10 visualizações7 páginas

    Us 5663409

    Enviado por

    kevin_ru_icq9831
    United States Patent Blackburn et aI. Patent Number: Date of Patent: PROCESS FOR THE PREPARATION OF 3(METBYltho) PROP ANAL AND 2BYDROXY-4-(METBYLTHIO) BUTANENITRILE. 260 / 601 FOREGN PATENT DOCUMENTS OTHER PUBLICATIONS.

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    United States Patent 119 Blackburn et al. (54) 073) 031 Ry ray (si) 1821 (8) so PROCESS FOR THE PREPARATION OF 3- (METHYLTHIO) PROPANAL AND 2 HYDROXY-4(METHYLTHIO) ‘BUTANENITRILE Inventors: Thomas F. Blackburn, Chesterfield; Paul F. Pellegrin, St. Louis, both of Mo. ‘Assignee: Novus International, Inc. St. Louis, Mo. Appl. No. 476356 Filed: Jun. 7, 1995 Int. CLS COTE 253/30; COTC 253/00; COTE 319/18; COTC 323722 = $8881; 568/41 we S681; 558/351 US. Cl - Field of Search scene References Cited US. PATENT DOCUMENTS 11950 971950 21951 e951 271952 11983, 41954 2521677 21523,633 21542,768 2557.913 2,584,496 21626282 21676190 2748745 5/1956 2716996 1957 2/938053 5/1960 3438868 4/1969 3'529.940 9/1970 3574766 4ng7h 3,690,148 10/1972 3,833,651 971974 3878087 4/1975 ‘oas2% 9n977 4225516 9/1980 4319047 3/1982 3352837 1071994 FOREIGN PATENT DOCUMENTS 797873 10/1968 Canada Vander Weele Pietson etal. non Gresham etal. Livak etal. ietson eta ornencn Cunningham et al. Bemard etal nv Blake et al. ant eta. Blake et Sawaki eta Shima eta. Meyer et al Dareas et al Ouchi etal. Biola eta... Komora et al. Hsu etl US005663409A (1) Patent Number: 5,663,409 145] Date of Patent: Sep. 2, 1997 820968 9/1969 Canada 97673 3/1951 France 504018 1/1975 Japan ‘867966 5/1961 United Kingdom 986198 3/1965 United Kingdom 1150252 4/1969 United Kingdom wn CO7C 149/14 1162054 8/1969 United Kingdom aru. COTC 149/14 10/1969 United Kingdom wavvinw CO7C 149/14 12/1969 United Kingdom war. COTE 145/14 11774701970 United Kingdom samen CO7C 149/14 1510256 5/1978 United Kingdom ....... CO7C 149/14 OTHER PUBLICATIONS Chemical Abstracts, vol. $3, No. 18, Sep. 25, 1959, Abstract No. 16940b for Z\Brzozowski, “Preparation of B-meth- yithiopropionaldchydes,” Rocaniki Chem., vol. 33, pp. 217-220 (1959), Chemical Abstracts, vol. 82, No. 3, Jan. 20, 1975, Abstract No. 16318p for Japanese Patent No. 74024890, Jun. 26, 1974, Chemical Abstracts, vol. 83, No. 1, Ju. 7, 1975, Abstract 'No. 9197 for Japanese Patent No. 74024046, Jun. 20, 1974. Derwent World Patent Index abstract for Japanese Patent 'No. No. 74024890, Jun, 26, 1974. Derwent World Patent Index Patent No. 74024046, Jun. 20, 1974, Z, Brrozowski, “Preparation of B-methylthiopropionalde- hydes.” Roceniki Chem., vol. 33, pp. 217-220, 91959). Primary Examine—Jobann Richter ‘Assistant Exaniner—Laura L, Stockton ‘Aomey, Agen, or Firm—Seanigen, Powers, Leavitt & Roedel 17) Catalytic processes for the preparation of 3-(methylthio) propanal and 2-hydroxy-4-(methylthio)butanenitrile using novel addition catalysts are disclosed. The novel addition catalysts include: nicotinamide, imidazole, benzimidazole, 2-fluoropyridine, _ poly-4-vinylpyridine, 4-dimethylaminopyridine, picoline and pyrazine. ABSTRACT 17 Claims, No Drawings 5,663,409 1 PROCESS FOR THE PREPARATION OF 3- (METHYLTHIO) PROPANAL AND 2- HYDROXY-4.(METHYLTHIO) BUTANENITRILE BACKGROUND OF THE INVENTION ‘The present invention relates to catalytic processes for the preparation of 3-(methylthio)propanal (hereinafter “MMP”) and 2shydroxy-4-(methylthio)butanenitrle (“HMBN"). More particularly, the present invention relates to processes for preparing MMP and HMBN using novel addition eata- lyst. MMP and HMBN are intermediates forthe manufacture of both di-methionine and 2-hydroxy-4-(methylthio) tuutanoic acid (“HMBA"), Methionine isan esseatil amino acid commonly deficient in grains used in animal feed compositions. IIMBA provides a source of methionine, and is widely used as a methionine supplement in enimal Teed formulations MMP is produced by the catalytic reaction between acrolein and methyl mercaptan. In a conventional process for the preparation of MMP, liquid acrolein and methyl rercaptan are introduced into a reactor containing liquid phase MMP and a suitable organic base which acts as an ‘lefin/mercaptan addition reaction catalyst. Reaction takes place in the liquid phase. Conventional organic base cata- Its forthe reaction between acrolein and methyl mereaptan include amines such as pyridine, hexamethylenetetramine and wiethylamine. The olefin/mescaptan addition reaction catalyst is typically combined with an organic acid such as acetic acid to inhibit polymerization of acrolein and improve product yiel. HMBN is subsequently produced by the addition reaction between MMP and hydrogen cyanide in the presence of a suitable addition reaction catalyst, which may inelude the cnganie bases used to catalyze the reaction between acrolein and methyl mercaptan. Methionine may be produced by reacting HMBN with excess ammonia under high pressure to produce 2-amino-4-(methylthio)butanenitile and subse- quently hydrolyzing the product using a mineral acid to form ‘ethionine. Alternatively, methionine may be produced by reacting MMP with ammonium carbonate to form « hydan- toin and subsequently hydrolyzing the hydantoin with a base to form methionine, HMBA may be produced by hydroly2- ing HMBN using a mineral acid. Pyridine has proven to be an effective addition catalyst used in preparing both MMP and MBN. However, it would be highly beneficial to identify effective alternative addition reaction catalysts for the preparation of these valuable intermediates. ‘SUMMARY OF THE INVENTION Among the several objects of the present invention are the provision of a process for the preparation of MMP by the catalytic reaction between acrolein and methyl mercaptan; the provision of such a process which provides a high MMP reaction yield; the provision of such a process in which the degradation of MMP and production of high molecular ‘weight by-products is maintained at acceptably low levels; the provision of such a process which can produce high {quality MMP that can be used directly, without the need for further purification, in the preparation of methionine or HMBA; the provision of a process for the preparation of HIMBN by the catalytic reaction between the MMP reaction product and hydrogen cyanide; the provision of such a 2s 2» 4% 58 © 6 2 process which provides a high HMBN reaction yield; and the provision of such a process in which the catalyst remain- ing in the MMP reaction product may be further used to catalyze the reaction between MMP and hydrogen cyanide to produce HMBN. Briefly, therefore, the present invention is directed to a process for the manufacture of MMP. The process comprises reacting methyl mercaptan with acrofein in a reaction zone in the presence of a novel olefin/mercaptan addition reaction ‘catalyst. The novel catalyst comprises at least one organic base selected from the group consisting of nicotinamide, imidazole, benzimidazole, 2-fluoropyridine, 4-dimethylaminopyridine, picoline and pyrazine. It has been further discovered that the novel olefin/ ‘mercaptan addition reaction catalyst used in catalyzing the reaction between acrolein and methyl mercaptan are also useful in catalyzing the reaction between MMP and hydro- ¢gen cyanide to produce HMBN. Thus, the present invention is further directed to a process for the manufacture of HMBN comprising reacting MMP with hydrogen cyanide in the presence of an addition reaction catalyst. The addition reaction catalyst comprises at least one organic base selected from the group consisting of nicotinamide, imidazole, benzimidazole, 2-fluoropyridine, poly-4-vinylpyridine, 4-dimethylaminopyridine, picoline and pyrazine. Jn accordance with another embodiment of the present invention, the novel addition catalyst disclosed herein are used to first catalyze the reaction between methyl mercaptan, and acrolein to produce an intermediate reaction product, mixture comprising MMP and the novel catalyst. Then, ‘without prior separation of the catalyst from the MMPin the intermediate reaction product mixture, the MMP reaction product is reacted with hydrogen cyanide to produce HMBN, Other objects and features ofthis invention will be in part apparent and in part pointed out hereinafter. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Tn accordance with the present invention, MMP is pro- dduced by the reaction between acrolein and methyl mercap- tan in the presence of novel olefin/mercaptan addition cata- lysts. MMP in the reaction product mixture may then be reacted with hydrogen cyanide to produce HMBN using the novel catalysts present in the MMP reaction product mixture as addition reaction catalyst in the cyanidation reaction, “The catalytic reaction between acrolein and methyl mer- caplan to produce MMP is well-known and, in the practice Of the present invention, this reaction can be casried out in any suitable fashion without particular limitation 10 the various process conditions employed. For example, acrolein ‘vapor may be absorbed in a liquid reaction medium con- taining recycled MMP product. The acrolein absorbed in the liquid reaction medium is reacted with methyl mercaptan in the presence of an olefin/mercaptan addition reaction cata- lyst within the reaction zone of a suitable reactor. Methyl ‘mercaptan is added to the liquid reaction medium in an amount at least substantially stoichiometrcally equivalent to the acrolein on a molar basis. A slight excess of methyl rmereaptan may be employed, Preferably, about 1 to about 1.02 moles of methyl mercaptan are introduced into the reaction zone for each mole of acrolein present in the liquid reaction medium. The methyl mercaptan and acrolein can be {introduced into the liquid reaction medium either simulta- neously or successively. The olefin/mercaptan addition reac- tion catalyst may be present either completely or partially in 5,663,409 3 the MMP or can be introduced into the liquid reaction ‘medium entirely or partially along with the acrolein and ‘methyl mercaptan, ‘The temperature of the reaction is desirably maintained within the range from about 30° to about 70° C. Reaction 5 pressure is not critical and may vary within wide limits. However, in order to simplify the reaction apparatus. it is preferred that the reaction be conducted at about atmo- spheric pressure or at only moderately reduced or elevated pressure, ‘The reaction between acrolein and methyl mercaptan may be conducted in either a continuous or batchwise fashion. In a batch process, acrolein vapor or liquid may be added to ‘methyl mercaptan in substantially molar equivalent quanti- ties, Alternatively. acrolein and methyl mercaptan may be simultaneously introduced at substantially stoichiometri- cally equivalent rates of addition into a liquid reaction ‘medium comprising MMP. The reaction medium for a given batch is conveniently provided for a given batch by leaving a heel of MMP in the reactor from a previous batch. Thus, ‘the batch reactor may be operated in a semi-continuous ‘mode in which the acrolein and methyl mercaptan are introduced at a substantially constant rate over a significant portion of the batch cycle, and the reaction product is periodically withdrawn from the reactor, leaving a heel for the next batch. Fully continuous processes are described, for example, in Biola US. Pat. No. 4.225.516 and Hsu et al. US. Pat. No. 5.352.837, both of which are expressly incorporated herein by reference. As described in Hsu et al., the continuous reaction may be carried out by introducing acrolein vapor and methyl mercaptan into a flowing MMP reaction medium in either a co-current or countercurrent gas/liquid contact, zone. Alternatively, the initial reaction may be carried out in a stirred tank reactor having an external cooler through ‘which the reaction mixture is circulated Ifthe reaction is not completed in the residence time afforded in the initial ‘gas/liquid contact zone, the MMP reaction medium contain- ing unreacted acrolein and methyl mercaptan is forwarded to a second reactor (e.g. a plug flow reactor ora batch holding tank) for completion ofthe reaction. Preferably, the reaction temperature of the reaction does not exceed about 70° C. in any of the reaction zones. Olefin/mereaptan addition catalysts for the commercial production of MMP are preferably evaluated on the basis of several criteria, including (1) conversion and yield of MMP: (2) reaction kinetics; and (3) tendency to catalyze unwanted side reactions which produce high molecular weight by-products and decrease product purity, both during the ‘MMP reaction and during subsequent storage of the MMP reaction product. Furthermore, such catalysts are preferably useful in further catalyzing the reaction between MMP and hhydrogen cyanide to produce HMBN so that the MMP reaction product mixture containing the addition catalyst can be directly treated with hydrogen cyanide to produce MBN, without intervening purification It has been discovered that certain organic bases which previously had not been recognized as viable olefin! ‘mercaptan addition reaction catalyst may advantageously be used to catalyze the reaction between acrolein and methyl ‘mercaptan to form MMP. Accordingly. the novel catalyst of the present invention includes at least one onganic base selected from the group consisting of nicotinamide. imidazole. benzimidazole, 2-Auoropyridine. 65 4-dimethylaminopyridine, picoline (e.g.. 2-picoline, 3-picoline and 4-picoline) and pyrazine. 2s 20 3s 45 0 5s © 4 Each of these organic bases may suitably be used as olefin/mercaptan addition catalyst in the commercial pro- duction of MMP. However, with reference to the catalyst evaluation criteria identified herein, some of these organic bases have demonstrated greater overall performance and effectiveness than others. In accordance with a more pre- ferred embodiment of the present invention, the olefin! ‘mercaptan addition catalyst comprises at least one organic base selected from the group consisting of imidazole, ben imidazole and picoline. In addition to the aforementioned organic bases. we have considered other organic bases as olefin/mercaptan addition reaction catalyst for use in the preparation of MMP. includ~ ing poly-4-vinylpyridine, tripropylamine, tibutylamine, triphenylamine, tibenzylamine, toctylamine, sodium nico- tinamide and 3-fuoropyridine. Tn addition to these base catalysts. we have also contemplated using certain salts as ccaalyst for promoting the reaction between acrolein and ‘methyl mercaptan, including alkali metal acetates, molyb- dates and formates, either alone or combined with a crown ther or quaternary ammonium salt to enhance the solubility of the salt anion in the MMP reaction mixture, zinc acetate, Zinc carbonate and salts of ethylenediaminetetraacetic acid. Furthermore, we have examined the use of other compounds, viz.. p-toluenesulfonic acid, 4-aminobutyric acid and palladium chloride, as catalysts in the preparation of MMP. ‘The olefin/mercaptan addition reaction catalyst should be present.in the liquid reaction medium in an amount suficient to effectively catalyze the reaction between acrolein and ‘etinyl mercaptan. Preferably, the molar ratio of the catalyst to methyl mercaptan present in the reaction zone is from about 0.001 to about 0.02. It should be noted that some of the novel olefin’mercaptan addition reaction catalyst disclosed herein (e.g.. nicotinamide, imidazole, benzimidazole and poly- vvinylpyridine) are solids at typical MMP reaction terapera- tures. If sufficiently soluble, such solid catalysts may be suitably employed by dissolving the catalyst in the liquid MMP reaction mixture. If the catalyst is insufficiently soluble, a minimal amount of a suitable solvent (eg.. water) ‘may be added to the reaction mixture asa catalyst solubility aid, or the catalyst may simply be suspended in the reaction mixture, The novel olefin/mercaptan addition reaction catalysts described herein are preferably combined with an organic ot inorganic acid in the reaction zone. The presence of an acid is believed to moderate the basicity of the organic liquid reaction medium, thereby inhibiting undesirable base- catalyzed side reactions which decrease MMP quality. Moreover. the acid may enhance the solubility of solid catalysts in the liquid MMP reaction mixture. A variety of organic acids may be used, including acetic acid, formic acid, citric acid, short-chain fatty acids and organic sulfo- acids (c.g., tifluoromethanesulfonic acid). Suitable inor- ganic acids include mineral acids such as sulfuric and phosphoric acid. Due to commercial availability and rela- tively low cost, acetic acid is preferred. The molar ratio of ‘organic base to acetic acid introduced into the reaction zone is typically from about 0.5 to about 2.0, Preferably. in order to ensure that base-catalyzed side reactions are sufficiently inhibited, the molar ratio of organic base to acetic acid introduced into the reaction zone is from about 0.5 to about 1.0. Where one or more of the aforementioned bases is ‘combined in the reaction zone with a mineral acid, the ‘mineral acid is preferably sulfuric acid or phosphoric acid. ‘The molar ratio of the organic base to the mineral aci 5,663,409 5 {introduced into the reaction zone is preferably from about 1 to about 50. When one of the organic bases disclosed herein is combined with an organic or inorganic acid in the reaction zone, the liquid reaction medium preferably contains between about 0.2 and about 0.75 weight percent of the ‘organic base/acid combination. MMP reaction product may be used directly for the ‘preparation of HMBN without prior distillation for removal of either high boiling or low boiling impurities.’This not only saves the capital and operating expense of distillation, but also avoids the yield losses inevitably resulting from the formation of additional high boilers in an MMP distillation column. HMBN may be produced by reacting the MMP reaction product with hydrogen cyanide in the presence of a suitable addition reaction catalyst. Advantageously, it has been further discovered that nicotinamide, imidazole, benzimidazole, 2-fluoropyridine, poly-4-vinylpyridine, 4-dimethylaminopyridine, picoline and pyrazine may serve a addition reaction catalyst in the production of HMBN. ‘Thus, in accordance with a preferred embodiment of the present invention, it is possible to first prepare MMP by reacting methyl mercaptan with acrolein in a reaction zone in the presence of one of the novel olefin/mercaptan addition reaction catalysts disclosed herein, either alone or in com- bination with a suitable organic or inorganic acid, to produce an intermediate reaction product mixture containing MMP ‘and the catalyst. Thereafter, and without prior separation of the catalyst from the MMP in the intermediate reaction product mixture, the MMP can be directly converted to HMBN by reacting the MMP with hydrogen cyanide. ‘The catalytic reaction between MMP and hydrogen cya- hide to produce HMBN is well-known and, in the practice of the present invention, this reaction can be carried out in ‘any suitable fashion without particular limitation to the ‘various process conditions employed. The MMP product, ‘ay be reacted with hydrogen cyanide in either acontinuous ‘or batchwise reaction system. Preferably, hydrogen cyanide is preseat in a slight molar excess of about 2 percent relative to MMP. The temperature of the cyanidation reaction is desirably maintained within the range from about 30° to about 70° C., preferably from about 50° to about 70° C. As in the MMP reaction, the pressure maintained during the ‘yanidation reaction isnot critical and may vary within wide limits, but preferably is close to atmospheric pressure. ‘Due to their overall effectiveness as catalysts for both the ‘lefin/mercaptan addition reaction and the reaction between ‘MMP and hydrogen cyanide, the addition catalyst used to prepare HMBN in this fashion preferably comprises at least ‘one organic base selected from the group consisting of imidazole, benzimidazole and picoline. ‘The MMP and hydrogen cyanide must be reacted in the presence of a sufficient amount of addition catalyst to effectively promote the cyanidation reaction. For some cats- lyst systems, a greater quantity of addition catalyst may be ‘employed during the cyanidation reaction than is present aa idee ©) 2Phaorpyidine! on a1 ‘etic acd (5). 3-Fhuompyiioe 02 a1 sete seid (0) ‘Tiprpylaminwscede aca! a1 o1 wate U) “Tabuylamine/acei acid (U) 1 os ‘Tiplenylamie (U) 1 al Tipberpaminecrtic aid (U)—

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